| At present,due to the objective environmental problems and the increase in energy demand,the development and utilization of new clean energy materials is the key to solving the problem.The preparation and performance optimization of the catalyst are the top priority of this problem.According to reports in the literature,various two-dimensional materials,such as metal organic framework compound(MOF)flakes,covalent organic framework(COF),oxide flakes,and supramolecular flakes,can improve the performance of electrochemical catalysis.Metal porphyrins and phthalocyanines can be reduced through metal reduction and ligand reduction,so that they have a certain reduction ability.At the same time,porphyrins and phthalocyanines themselves have a conjugated structure of 18π electrons,which enables them to stabilize electrons.Therefore,their metal complexes It has good electrocatalytic hydrogen evolution properties.As a result,metal phthalocyanine and corrol are made into two-dimensional materials to further improve electrocatalytic performance.In this thesis,by designing and synthesizing a variety of compounds modified with different groups,a simpler method is used to prepare nanocrystals to improve the electrocatalytic hydrogen evolution performance of metalloporphyrin derivatives,as follows:(1)We use three β-tert-butyl-metal phthalocyanine complexes(M=Co(III),Ni(II),Cu(III))as key precursors.The self-assembly of phthalocyanine molecules is controlled by using different kinds of solvents and ultrasonic conditions,and they are made into phthalocyanine nanosheets with a thin-layer structure to test its electrochemical hydrogen evolution performance and stability.When the phthalocyanine self-assembled into nanosheets,it can significantly improve its electrochemical catalytic hydrogen evolution performance.(2)Three examples of cobalt complexes were obtained by introducing different numbers of pyrene groups at the meso site through Suzuki coupling.The structures of three examples of cobalt complexes were preliminarily characterized by nuclear magnetism.The cyclic voltammetry of cobalt complexes was tested by electrochemical workstation.(CV)curve and differential pulse voltammetry curve(DPV).Use ultraviolet spectroscopy to characterize the spectral properties of cobalt.Furthermore,three kinds of cobalt corrole were made into nanocrystals as catalysts,and they were supported on multi-walled carbon nanotubes(m WCNTs),which showed good application performance for electrochemical hydrogen evolution.The morphology of the catalyst and the electrochemical hydrogen evolution ability are adjusted according to the number and position of the pyrene ring.(3)On the basis of(2),three kinds of copper pyrene modified with one or two pyrene groups were introduced at different positions by Suzuki coupling,and basic characterization was carried out by ultraviolet and nuclear magnetic compounds,and the CV was tested for the study of its electronic structure.And DPV.Use ultraviolet spectroscopy to characterize its spectral properties.In terms of electrochemical catalytic hydrogen evolution,three cases of copper corrole were made into nanocrystals as a catalyst to further explore its electrocatalytic hydrogen evolution performance and explore its morphology.(4)The hydroxymethyl phenyl group was introduced into three kinds of metal cobalt and copper corrole by Suzuki coupling,and 3 cases of metal corrole were synthesized.And its structure was fundamentally characterized,and its ultraviolet,nuclear magnetic and electrochemical properties were tested.The three kinds of corrole complexes were made into nano-crystallite catalysts by the same method as above,and their electrocatalytic hydrogen evolution performance was explored and morphological tests were carried out.In summary,the simple preparation method and enhanced catalytic performance may help future material design and applications,and compared with amorphous metal phthalocyanine and corrole molecules,highly ordered metal phthalocyanine nanosheets And metal corrole microcrystals can be used as more efficient electrochemical catalysts.Considering that phthalocyanine-based materials have a wide range of applications,the metal corrole ring has a smaller ring cavity that is easy to modify,which may help future material design and applications. |
